CN1272889A - Stainless steel product having excellent antimicrobial activity and method for production thereof - Google Patents
Stainless steel product having excellent antimicrobial activity and method for production thereof Download PDFInfo
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- CN1272889A CN1272889A CN99800934A CN99800934A CN1272889A CN 1272889 A CN1272889 A CN 1272889A CN 99800934 A CN99800934 A CN 99800934A CN 99800934 A CN99800934 A CN 99800934A CN 1272889 A CN1272889 A CN 1272889A
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- stainless steel
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- microbial property
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- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 87
- 239000010935 stainless steel Substances 0.000 title claims abstract description 78
- 230000000845 anti-microbial effect Effects 0.000 title claims abstract description 76
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 229910052709 silver Inorganic materials 0.000 claims abstract description 42
- 239000004332 silver Substances 0.000 claims abstract description 42
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000009749 continuous casting Methods 0.000 claims abstract description 14
- 238000005266 casting Methods 0.000 claims abstract description 6
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 claims description 34
- 229910052720 vanadium Inorganic materials 0.000 claims description 18
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 18
- 239000011651 chromium Substances 0.000 claims description 17
- 229910052804 chromium Inorganic materials 0.000 claims description 15
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 239000005864 Sulphur Substances 0.000 claims description 9
- 230000004927 fusion Effects 0.000 claims description 8
- 238000005098 hot rolling Methods 0.000 claims description 6
- 235000007164 Oryza sativa Nutrition 0.000 claims description 5
- 238000005097 cold rolling Methods 0.000 claims description 5
- 235000009566 rice Nutrition 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 240000007594 Oryza sativa Species 0.000 claims 1
- 229910000831 Steel Inorganic materials 0.000 abstract description 49
- 239000010959 steel Substances 0.000 abstract description 49
- 230000007797 corrosion Effects 0.000 abstract description 29
- 238000005260 corrosion Methods 0.000 abstract description 29
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 abstract description 12
- 229910001923 silver oxide Inorganic materials 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 22
- 241000894006 Bacteria Species 0.000 description 18
- 238000012360 testing method Methods 0.000 description 13
- 230000001580 bacterial effect Effects 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 9
- 229910000734 martensite Inorganic materials 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 8
- 239000004615 ingredient Substances 0.000 description 8
- 238000000137 annealing Methods 0.000 description 7
- 239000010960 cold rolled steel Substances 0.000 description 7
- 238000005498 polishing Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229910052946 acanthite Inorganic materials 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 230000002688 persistence Effects 0.000 description 5
- 229940056910 silver sulfide Drugs 0.000 description 5
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 241000209094 Oryza Species 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 230000000968 intestinal effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 239000010955 niobium Substances 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 229910020641 Co Zr Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910001566 austenite Inorganic materials 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 235000015097 nutrients Nutrition 0.000 description 2
- 230000007170 pathology Effects 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000009628 steelmaking Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- 229920001817 Agar Polymers 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 1
- 206010016952 Food poisoning Diseases 0.000 description 1
- 208000019331 Foodborne disease Diseases 0.000 description 1
- 239000001888 Peptone Substances 0.000 description 1
- 108010080698 Peptones Proteins 0.000 description 1
- 241000607142 Salmonella Species 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- AIUDWMLXCFRVDR-UHFFFAOYSA-N dimethyl 2-(3-ethyl-3-methylpentyl)propanedioate Chemical class CCC(C)(CC)CCC(C(=O)OC)C(=O)OC AIUDWMLXCFRVDR-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000012854 evaluation process Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000007431 microscopic evaluation Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 235000019319 peptone Nutrition 0.000 description 1
- 229940066779 peptones Drugs 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- -1 silver ions Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Heat Treatment Of Sheet Steel (AREA)
- Heat Treatment Of Steel (AREA)
Abstract
A stainless steel product having excellent corrosion resistance, antimicrobial activity and durability which may be produced by providing a stainless steel product containing 10 wt.% or more of Cr, incorporating 0.0001 to 0.30 wt.% and optionally 0.0001 to 1.0 wt.% of V into the stainless steel product, and further incorporating and dispersing therein a silver oxide in an amount of 0.0005 wt.% or more and not more than 1.1 times that of the silver contained in the steel product, and a method for the production thereof. It is desirable for uniformly dispersing the aforementioned silver oxide that the casting of a molten steel is carried out by a continuous casting at a pouring speed of 0.8 to 1.6 m/min. The process for producing this stainless steel is also disclosed.
Description
Technical field
The present invention relates to stainless steel.More specifically, the present invention relates to have the stainless steel of anti-microbial property, this stainless steel is suitable for as the relevant equipment of life, galley equipment for example, and medical facilities, electrical equipment, chemical industry equipment, and building materials the invention still further relates to this stainless manufacture method.Stainless form of the present invention comprises sheet material, band, tubing and wire rod.
Background technology
Be well known that silver and copper are inhibited to the growth of pathology bacterium (representational is intestinal bacteria and Salmonellas), and can prevent effectively by the caused food poisoning of pathology bacterium.
At present, proposed to use the material with bacteria growing inhibiting effect (below be called antimicrobial characteristic) of these metals.For example in the flat 8-49085 of JP-A-, disclose stainless steel, on stainless steel surface, formed the metal level or the alloy layer of the chromium that contains silver and/or copper, titanium, nickel, iron etc. by magnetron sputtering with excellent anti-microbial property.In this steel plate, be preferably formed as the metal level or the alloy layer that contain 19-60% (weight) silver.
In the flat 8-156175 of JP-A-, disclose a kind of coating that can bacteria growing inhibiting and contained the steel plate of Silver pigments.
But, in the above-mentioned method that on surface of steel plate, forms the metal level that comprises metal or alloy layer with anti-microbial property, and comprise in the method for pigment of metal with anti-microbial property in coating, owing to calendering and surface finish are peeled off the layer that comprises the metal with anti-microbial property or come off, and problem is that this result is unpredictable.In application, for example be used as the steel plate of the washing machine inwall of wearing and tearing continuously, and as the kitchen tools steel plate that need often clean, existing problem is that anti-microbial property can not keep for a long time.In aforesaid method, the step that needs additional manufacturing steel plate is to form coating, metal level and alloy layer.In addition, when making,, consider that from the angle of cost this is disadvantageous owing to the amount of coating, metal level and the alloy layer of unit weight follows the surface-area of unit weight to increase than steel sheet.
In order to address the above problem, as in the flat 8-104953 of JP-A-, disclosing by adding the austenitic stainless steel of 1.1-3.5% (weight) copper with the anti-microbial property that is enhanced, as in the flat 8-104952 of JP-A-, disclosing by adding the be enhanced Martensite Stainless Steel of anti-microbial property of 0.3-5% (weight) copper, as in the flat 9-170053 of JP-A-, disclosing by the be enhanced ferritic stainless steel of anti-microbial property of interpolation 0.4-3.0% (weight) copper.
But in the disclosed technology, cupric ion must leach to produce anti-microbial property from surface of steel plate in the flat 8-104953 of JP-A-, flat 8-104952,9-170053.It is owing to destroyed passivation layer leaching point that copper leaches with ionic species, so solidity to corrosion significantly reduces, though improved anti-microbial property.Therefore, for the cupric stainless steel, be difficult to have simultaneously anti-microbial property and solidity to corrosion.
The objective of the invention is provides a kind of stainless steel and manufacture method thereof by solving prior art problems.Stainless steel of the present invention has excellent anti-microbial property and solidity to corrosion, and has excellent anti-microbial property continuously, even after carrying out the conventional surface working processing of using as polishing.
Description of the invention
Have excellent anti-microbial property and corrosion proof stainless steel plate in order to study, the inventor has furtherd investigate the chemical ingredients on stainless steel plate surface and the relation between the anti-microbial property by abundant operational analysis instrument, and these analytical instrument for example are emission Auger Electronic Speculum and electron beam microscopic analyzer.As a result, reach at stainless steel surface and the inner silver that disperses optimum content in stainless steel by the silver that adds optimum quantity, the inventor finds can obtain to have the stainless steel of excellent anti-microbial property and excellent corrosion resistance.In addition, the inventor finds that continuous casting speed and vanadium add-on have remarkably influenced to the homodisperse of silver.Also have, the inventor finds to contain the steel of homodisperse best silver content wherein, as the steel part through mold pressing and polishing, and during as the steel surface of in use standing to clean and grind, has stable anti-microbial property.
The present invention is based on above-mentioned knowledge and further study and finish.
Therefore, a first aspect of the present invention is a kind of stainless steel with anti-microbial property, contains the above chromium of 10% (weight), the silver of 0.001-0.30% (weight), with the above silver suboxide of 0.0005% (weight), the content of this silver suboxide is below 1.1 times of silver content.
A second aspect of the present invention is a kind of stainless steel with anti-microbial property by first aspect, also contains the vanadium of 0.001-1.0% (weight).
A third aspect of the present invention is a kind of stainless steel with anti-microbial property by first aspect and second aspect, also contains the following sulphur of 0.015% (weight).
A fourth aspect of the present invention is that a kind of wherein silver content is counted more than 0.001% (weight) with stainless steel weight by the stainless steel with anti-microbial property of first aspect to the third aspect, and less than 0.05% (weight).
A fifth aspect of the present invention is a kind of stainless steel with anti-microbial property by second aspect, and wherein content of vanadium is 0.001-0.30% (weight) in stainless steel weight.
A sixth aspect of the present invention is a kind of stainless steel with anti-microbial property by first aspect to the five aspects, and wherein this stainless form is any in sheet material, band, tubing and the wire rod.
A seventh aspect of the present invention is a kind of method of making the stainless steel raw material, comprises the following steps: to control in the fusion stainless steel chromium content more than 10% (weight), the sulphur content that the silver content and 0.015% (weight) of 0.001-0.30% (weight) is following; And with 0.8-1.6 rice/minute casting speed continuous casting fused stainless steel.
A eighth aspect of the present invention is by the stainless method of the manufacturing of the 7th aspect, and wherein the fused stainless steel also contains 0.001-1.0% (weight) vanadium.
A ninth aspect of the present invention is the stainless method that has anti-microbial property by the manufacturing of the 7th aspect and eight aspect, also comprises hot rolling and cold rolling step.
Explained later limits the reason of the stainless chemical ingredients of the present invention.
Stainless chemical ingredients of the present invention is applicable to the stainless steel of austenitic stainless steel, ferritic stainless steel, Martensite Stainless Steel and other types.
The chemical ingredients of austenitic stainless steel is preferably as follows; Following following following phosphorus, the chromium of 10-35% (weight), the nickel of 6-15% (weight), the nitrogen of 0.001-0.1% (weight), the surplus of manganese, 0.1% (weight) of silicon, 2.0% (weight) of the carbon, 2.0% (weight) of 0.001-0.1% (weight) is the impurity of iron and association.In addition, in this austenitic stainless steel, can contain and be selected from one or more following elements: the zirconium below the niobium, 1.0% (weight) below the titanium, 1.0% (weight) below the aluminium, 1.0% (weight) below the tungsten, 0.3% (weight) below the copper, 0.30% (weight) below the molybdenum, 1.0% (weight) below 3.0% (weight), the carbon below the cobalt and 0.01% (weight) of 0.001-0.5% (weight).
The chemical ingredients of ferritic stainless steel is preferably as follows; Phosphorus below the manganese, 0.1% (weight) below the silicon, 2.0% (weight) below the carbon, 1.0% (weight) of 0.001-0.1% (weight), following nitrogen, the surplus of the chromium, 0.10% (weight) of 10-50% (weight) are the impurity of iron and association.In addition, in this ferritic stainless steel, can contain and be selected from one or more following elements: the tungsten below the copper, 0.30% (weight) below the zirconium, 1.0% (weight) below the niobium, 1.0% (weight) below the titanium, 1.0% (weight) below the molybdenum, 1.0% (weight) below the nickel, 3.0% (weight) below the aluminium, 1.0% (weight) below 0.3% (weight), the boron below the cobalt and 0.01% (weight) of 0.001-0.5% (weight).
The chemical ingredients of Martensite Stainless Steel is preferably as follows; Following following following phosphorus, the chromium of 10-19% (weight), the nitrogen of 0.001-0.1% (weight), the surplus of manganese, 0.1% (weight) of silicon, 2.0% (weight) of the carbon, 1.0% (weight) of 0.001-0.1% (weight) is the impurity of iron and association.In addition, in this stainless steel, can contain and be selected from one or more following elements: the copper below the molybdenum, 1.0% (weight) below the nickel, 3.0% (weight) below the zirconium, 3.0% (weight) below the tungsten, 1.0% (weight) below the niobium, 0.30% (weight) below the titanium, 1.0% (weight) below the aluminium, 1.0% (weight) below 1.5% (weight), the boron below the cobalt and 0.01% (weight) of 0.001-0.5% (weight).
According to the present invention, this stainless steel contains the above chromium of 10% (weight), and preferably this stainless steel has mentioned component, comprises the silver of 0.001-0.30% (weight), perhaps also contains the vanadium of 0.001-1.0% (weight).In addition, this stainless steel contains the above silver suboxide of 0.0005% (weight), and the content of this silver suboxide is below 1.1 times of silver content in the stainless steel (% (weight)).According to mentioned component, can obtain stable and very excellent anti-microbial property under the corrosion proof condition not reducing.
Chromium: more than 10% (weight)
With chromium content be defined as the above reason of 10% (weight) be if chromium content less than 10% (weight) then solidity to corrosion is poor.The upper limit of chromium content is not concrete to be limited, but considers from workability and manufacturing, below preferred 50% (weight).
Silver: 0.001-0.3% (weight)
Silver is most important element of the present invention, the inhibited and enhancing anti-microbial property to bacterial growth.Silver content is these effects that 0.001% (weight) can be observed silver when above, but when silver content surpassed 0.30% (weight), solidity to corrosion reduced and surface imperfection increase in course of hot rolling.In addition, it is disadvantageous adding a large amount of expensive silver from cost consideration.Therefore silver content is defined as 0.001-0.3% (weight).More preferably, silver content is less than 0.05% (weight).
Contained silver exists with the form of silver (Ag) particle, silver suboxide and silver sulfide in stainless steel.According to the inventor's understanding, this anti-microbial property of three kinds is followed successively by silver suboxide＞silver-colored particle＞silver sulfide, and therefore, the silver among the present invention exists to strengthen anti-microbial property with the form of silver suboxide mostly.
Anti-microbial property it be not immediately clear according to the specific reasons of the order of silver suboxide＞silver-colored particle＞silver sulfide, but, can suppose because high leaching yield silver suboxide presents high anti-microbial property because silver suboxide has the highest silver ions (having anti-microbial property) leaching yield.
Therefore, stainless steel of the present invention contains the above silver suboxide of 0.0005% (weight), and the content of silver suboxide is below 1.1 times of silver (weight percentage) in the stainless steel.When the silver suboxide of above-mentioned content is scattered in the stainless steel equably, silver suboxide always is present on the steel surface, promptly not only when shipment on the steel surface, and after polishing, machining and the grinding also in its surface, and in use because wearing and tearing and on the new surface that exposes.Therefore, suppress the growth of bacterium, and strengthened anti-microbial property.This silver suboxide for example is AgO or Ag
2O.
More than in steel plate, containing 0.0005% (weight) have the silver suboxide of excellent anti-microbial property the time, can obtain good antimicrobial property.When silver suboxide content during less than 0.0005% (weight), can not expect to have the effect of enough bacteria growing inhibitings, therefore the lower limit with the content of silver suboxide is defined as 0.0005% (weight).On the contrary, when the content of silver suboxide surpassed 1.1 times of silver content in the stainless steel, silver suboxide was easy to be gathered in crystal boundary etc. and locates, and tends to form thick oxide compound, the result, and solidity to corrosion reduces.In order to make full use of the anti-microbial property of silver suboxide, the upper content limit of silver suboxide is defined as below 1.1 times of silver (weight percentage) in the stainless steel.Need not the silver suboxide in the stainless steel of the present invention is defined as particular form, still,, be preferably below 500 microns because the silver oxide particle above 500 microns can make solidity to corrosion and processibility reduce.
By the silver suboxide amount of inclusion analysis that makes the electricity consumption extracting process, perhaps measure on the section at random at the steel sample of choosing by field emission Auger Electronic Speculum or electron beam microscopic analysis to produce in the measurement stainless steel of the present invention.
In the present invention, except the silver of above-mentioned scope, preferably contain the vanadium of 0.001-1.0% (weight).Measuring result owing to add vanadium to the influence of the anti-microbial property of stainless steel BA (clean annealing) product surface and 1.0 mm thick centers is shown in Fig. 1.This BA product is to be made through the following step by the stainless steel ingot of the 16.2%-Cr of the silver that contains 0.042% (weight): hot rolling, annealing hot-rolled steel sheet (850 ℃ * 60 seconds), cold rolling and clean annealing (850 ℃ * 60 seconds).No matter the add-on of vanadium can obtain stable anti-microbial property, still, in contrast, in the surface, when the add-on of vanadium during less than 0.001% (weight), anti-microbial property reduces in the center of product made from steel.Believe that this reason is the effect owing to so-called " dispersion agent ", this effect can suppress silver-colored particle, silver suboxide and silver sulfide significantly and make its part accumulate in steel plate inside center place.When content of vanadium is 0.001% (weight) when above, can obtain the constant antibacterial effect on the steel surface.In contrast, when content of vanadium surpassed 0.30% (weight), above-mentioned effect was promptly saturated, and when content of vanadium surpassed 1.0% (weight), processibility and solidity to corrosion were tended to reduce.Therefore, the content of vanadium scope is preferably 0.001-1.0% (weight).More preferably, scope is 0.001-0.30% (weight), is most preferably 0.01-0.25% (weight).
Stainless steel of the present invention is made up of as surplus the chemical ingredients of above-mentioned scope and iron and accompanying impurities.
Because steel of the present invention can be made by any known steel making method, therefore need not to limit manufacture method.For example, preferred manufacture method is to carry out secondary refining by SS-VOD (powerful stirring vacuum oxygen decarburization) after with steel-making steps such as converter, electric furnaces.
According to the present invention, make the fused stainless steel by known method for making steel, wherein this fusion stainless steel has the stainless steel composition, contains the above chromium of 10% (weight), the silver that also contains 0.001-0.30% (weight) perhaps also contains the vanadium of 0.001-0.1% (weight).The molten steel that available known castmethod will so be made is made the steel raw material, but from production efficiency and quality, preferably uses continuous casting.
In continuous casting, for refinement in steel and the silver suboxide more than the homodisperse 0.0005% (weight), with continuous casting speed be defined as 0.8-1.6 rice/minute.Follow definite continuous casting speed, the sulphur content in the fusion stainless molten steel is defined as below 0.015% (weight), more preferably is below 0.010% (weight).
When continuous casting speed during less than 0.8 meter/minute, the silver oxide particle chap is big, and solidity to corrosion reduces, and therefore is difficult to obtain stable anti-microbial property.On the contrary, when continuous casting speed surpasses 1.6 meters/minute, be difficult to carry out stable casting, and the above silver suboxide of 0.0005% (weight) can not be evenly distributed in the steel.Therefore, silver suboxide can not be distributed in the steel surface equably, and in use can not obtain stable anti-microbial property.Therefore the continuous casting speed in the casting process be preferably 0.8-1.6 rice/minute.
In the scope more than silver suboxide is 0.0005% (weight) and be under the condition below 1.1 times of the silver (weight percentage) in the stainless steel, follow continuous casting speed be 0.8-1.6 rice/minute, sulphur content in the fusion stainless steel is below 0.015% (weight), more preferably below 0.010% (weight).Can adjust sulphur content in the fusion stainless steel by known method of refining, and not limit concrete grammar, still, be preferred by the sulfur method that adds ferrosilicon and calcium cpd in converter and/or VOD stove.
When the sulphur content in the fusion stainless steel surpassed 0.015% (weight), the amount by the silver sulfide that forms with the silver reaction increased, and makes the anti-microbial property reduction because the amount of the silver suboxide with excellent anti-microbial property that produces reduces.Therefore, in order to obtain excellent anti-microbial property, the sulphur content in molten steel is preferably below 0.015% (weight).
According to the present invention, by fusion stainless steel, make the steel raw material by continuous casting (preferably continuous casting) under these conditions, and if desired, it is heat-treated in preset temperature after hot rolling with mentioned component, obtain the hot-rolled steel sheet of given thickness thus.If desired, hot-rolled steel sheet is annealed at 700 ℃-1200 ℃, and be used for desirable purposes as hot-rolled steel sheet or by the cold-rolled steel sheet with given thickness of cold rolling processing gained subsequently.This cold-rolled steel sheet preferably passes through 700-1200 ℃ of annealing, and makes by pickling if desired.
Brief description of drawings
Fig. 1 is that explanation is at the reduced rate of surface of steel plate and center bacterial count and the curve of the relation between the content of vanadium.
Realize best mode of the present invention
Embodiment
By continuous cast method, by the stainless steel that makes through steel-smelting technology, prepare the ingot blank of 200 mm thick, and with this ingot blank heating and hot rolling, thereby obtain the hot-rolled steel sheet of 4 mm thick with the chemical ingredients shown in table 1 and the table 2 with different casting speeds.Then, it is cold rolling that this hot-rolled steel sheet is annealed and carried out after pickling at 700-1200 ℃, obtains the cold-rolled steel sheet of 0.8 mm thick thus.Through this cold-rolled steel sheet of annealing, and when needs through overpickling, make cold-rolled steel sheet with different surfaces smooth finish.The annealing temperature of this cold-rolled steel sheet is as follows: for austenitic stainless steel is 1000-1200 ℃, is 800-1100 ℃ for ferritic stainless steel, is 750-1000 ℃ for Martensite Stainless Steel.Some stainless steels are carried out polished finish, thereby make the steel plate of #320 and #400 surface smoothness based on the R6001 of Japanese Industrial Standards (below be called JIS).
The annealing cold-rolled steel sheet is carried out the assessment of solidity to corrosion and anti-microbial property.For persistence and the weather resistance that confirms anti-microbial property, after the assessment solidity to corrosion, carry out the assessment of anti-microbial property once more.
The various appraisal procedures of carrying out are as described below.
(1) assessment anti-microbial property
According to assessing anti-microbial property by the defined adhesion of film method of study group to silver and other inorganic antibacterial reagent.Program to the adhesion of film method of the silver and the study group of other inorganic antibacterial reagent is described as follows.
1. use and contain 99.5% alcoholic acid absorbent cotton area is 25cm
2Test piece washing and degreasing.
2. intestinal bacteria are dispersed in the 1/500NB solution.(bacterial number is adjusted into 2.0 *
10
5-1.0 * 10
6Cfu (clone unit)/ml.1/500 NB solution is normally with not having
The nutrient broth medium (NB) that bacterium and purified water dilution are 500 times.This nutrient broth is situated between
Matter (NB) is 5 gram meat extracts, 5.0 gram sodium-chlor, 10.0 gram peptones and 1.000 normally
The mixture of the pure water of milliliter; Its pH value is 7.0 ± 0.2.)
3. go up with 0.5ml/25cm in test piece (3 every kind)
2Ratio cultivate and to contain bacterium
Solution.
4. cover the test piece surface with film
5. under being condition more than 90%, 35 ± 1.0 ℃ temperature and relative humidity (RH) trains
Support test piece 24 hours.
6. calculate survive thin by agar cultural method (35 ± 1.0 ℃, 40-48 hour)
Bacterium quantity.
Bacterium decrement with following formula definition is assessed anti-microbial property.
Decrement (%)=100 * (bacterial count after the bacterial count-assessment in the comparison)/(bacterial count in the comparison)
Bacterial count in the comparison is to use not argentiferous stainless steel plate to survive bacterial count after anti-microbial property assessment.The not argentiferous stainless steel plate that is used to assess is ferritic stainless steel SUS430 (grade of steel No 40), austenitic stainless steel SUS304 (grade of steel No 13) and Martensite Stainless Steel SUS410 (grade of steel No 23).The initial bacterial count of every kind of test piece is about 2.3 * 10
5The cfu/ test piece.Bacterial count after the assessment is the bacterial count that survives that calculates.
By using the persistence of having assessed anti-microbial property as the corrosion proof test piece of assessment according to above-mentioned identical method.
(2) assessment solidity to corrosion
By salt-drying-moist compound cycle test assessment solidity to corrosion.
A round-robin test comprises following processing 1 and handles 2.
1. with the 5.0%NaCl aqueous solution (temperature: 35 ℃) spray test piece 0.5 hour, store 1.0 hours 60 ℃ of temperature with below 40% humidity then.
2. under the wet condition of 40 ℃ of temperature and humidities more than 95%, store test piece 1.0 hours.
After every type steel is carried out the circulation of pre-determined quantity, measure the ratio of the lip-deep corrosion area of each test piece.Predetermined cycle index for ferritic stainless steel is 10 times, is 30 times for austenitic stainless steel, is 5 times for Martensite Stainless Steel.
Assessment result is shown in table 3 and 4.In the surface smoothness shown in the table, 2B and BA are the surface smoothness levels according to JIS G4305, and #320 and #400 are the polishing smooth finish levels according to JIS R6001.
Have excellent processibility and solidity to corrosion as the steel plate (embodiment of the invention) that can find out, prove the silver that contains scope of the present invention and silver suboxide from table 3 and 4.In addition, in evaluation process, proved excellent anti-microbial property, promptly reduced intestinal bacteria more than 99%, and the persistence of anti-microbial property is also excellent, in the test piece of solidity to corrosion assessment, reduce intestinal bacteria to be similar to aforesaid way.The persistence of anti-microbial property no matter steel plate surface smoothness how and can keep, and proved after polishing, to have enough anti-microbial properties.
No matter stainless type such as ferritic stainless steel, austenitic stainless steel and Martensite Stainless Steel all can confirm The above results.
On the contrary, in comparative example (outside scope of the present invention), stainless type no matter, colibacillary decrement all is little, and anti-microbial property reduces, perhaps the anti-microbial property after the assessment solidity to corrosion reduces and the persistence of anti-microbial property reduces.
Industrial applicability
The invention provides and have excellent anti-microbial property and do not reduce corrosion proof stainless steel, and Even carry out surface finish as the polishing after still keep anti-microbial property. Therefore, can obtain stainless Advantage in the steel commercial Application. Stainless steel of the present invention is suitable in humidity after moulding and polishing The application of the health aspect in the environment, for example application in kitchen and bathroom.
Table 1
| Grade of steel No. | Kind | Chemical composition (wt%) | Remarks | ||||||||||||||||||
| C | Si | Mn | P | S | Cr | N | Al | Mo | Cu | Ni | Ti | Nb | B | W | Co | Zr | Ag | V | |||
| 11 | Austenite | 0.05 | 0.31 | 1.05 | 0.03 | 0.006 | 18.2 | 0.04 | 0.002 | 0.04 | 0.30 | 8.30 | - | - | - | - | - | - | 0.042 | - | The inventive example |
| 12 | 0.05 | 0.30 | 1.04 | 0.03 | 0.005 | 18.2 | 0.04 | 0.002 | 0.04 | 0.31 | 8.20 | - | - | - | 0.01 | 0.12 | - | 0.035 | 0.04 | The inventive example | |
| 13 | 0.05 | 0.29 | 1.05 | 0.03 | 0.006 | 18.5 | 0.04 | 0.001 | 0.04 | 0.30 | 8.30 | - | - | - | - | - | - | - | - | Comparative example | |
| 14 | 0.04 | 0.33 | 1.03 | 0.03 | 0.005 | 18.2 | 0 04 | 0.002 | 0 04 | 0.31 | 8.30 | - | - | - | - | - | - | 0.009 | 0.01 | The inventive example | |
| 15 | 0.05 | 0.32 | 1.04 | 0.03 | 0.006 | 18.2 | 0.04 | 0.002 | 0.04 | 0.31 | 8.30 | - | - | - | - | - | - | 0.25 | 0.03 | The inventive example | |
| 16 | 0.05 | 0.30 | 1.02 | 0.03 | 0.005 | 18.2 | 0.04 | 0.002 | 0.04 | 0.30 | 8.30 | - | - | - | - | - | - | 1.03 | 0.02 | Comparative example | |
| 17 | 0.05 | 0 30 | 1.02 | 0.03 | 0.005 | 18.2 | 0.04 | 0.002 | 0.04 | 0.30 | 8.30 | - | - | - | - | - | - | 0.055 | 0.37 | The inventive example | |
| 18 | 0.05 | 0.30 | 1.01 | 0.03 | 0.008 | 18.3 | 0.03 | 0.001 | 0.04 | 0.30 | 8.15 | - | - | - | - | - | - | 0.40 | 0.03 | Comparative example | |
| 21 | Martensitic | 0.04 | 0.30 | 0.29 | 0.02 | 0.006 | 13.0 | 0.009 | 0.010 | - | - | 0.07 | - | - | - | - | - | - | 0.035 | - | The inventive example |
| 22 | 0.04 | 0.31 | 0.29 | 0.02 | 0.005 | 13.0 | 0.009 | 0.010 | - | - | 0.07 | - | - | - | 0.01 | 0.10 | - | 0.038 | - | The inventive example | |
| 23 | 0.04 | 0.31 | 0.32 | 0.02 | 0.005 | 13.1 | 0.010 | 0.010 | - | - | 0.06 | - | - | - | - | - | - | - | - | Comparative example | |
| 24 | 0.04 | 0.29 | 0.31 | 0.02 | 0.005 | 13.1 | 0.009 | 0.010 | - | - | 0.07 | - | - | - | - | - | - | 0.013 | 0.01 | The inventive example | |
| 25 | 0.04 | 0.30 | 0.30 | 0.02 | 0.006 | 13.2 | 0.009 | 0.010 | - | - | 0.06 | - | - | - | - | - | - | 0.22 | 0.02 | The inventive example | |
| 26 | 0.04 | 0.31 | 0.30 | 0.02 | 0.006 | 13.0 | 0.010 | 0.010 | - | - | 0.07 | - | - | - | - | - | - | 1.10 | 0.01 | Comparative example | |
| 27 | 0.31 | 0.45 | 0.35 | 0.03 | 0.005 | 13.1 | 0.025 | 0.002 | - | - | 0.25 | - | - | - | - | - | - | 0.037 | 0.01 | The inventive example | |
| 28 | 0.32 | 0.35 | 0.45 | 0.02 | 0.006 | 12.6 | 0.025 | 0.002 | - | - | 0.07 | - | - | - | - | - | - | 0.031 | 0.02 | The inventive example | |
| 29 | 0.33 | 0.34 | 0.44 | 0.02 | 0.006 | 12.6 | 0.025 | 0.002 | - | - | 0.07 | - | - | - | - | - | - | 0.031 | 0.38 | The inventive example | |
Table 2
| Grade of steel No. | Kind | Chemical composition (wt%) | Remarks | ||||||||||||||||||
| C | Si | Mn | P | S | Cr | N | Al | Mo | Cu | Ni | Ti | Nb | B | W | Co | Zr | Ag | V | |||
| 31 | Ferrite | 0.06 | 0.31 | 0.60 | 0.03 | 0.003 | 16.2 | 0.031 | 0.001 | - | - | 0.20 | - | - | - | - | - | - | 0.037 | - | The inventive example |
| 32 | 0.05 | 0.30 | 0.61 | 0.03 | 0.003 | 16.3 | 0.035 | 0.001 | - | - | 0.31 | - | - | - | 0.01 | 0.11 | - | 0.041 | 0.012 | The inventive example | |
| 33 | 0.05 | 0.30 | 0.58 | 0.03 | 0.003 | 16.2 | 0.022 | 0.070 | - | - | 0.12 | - | - | - | 0.01 | 0.15 | - | 0.020 | 0.021 | The inventive example | |
| 34 | 0.007 | 0.10 | 0.30 | 0.03 | 0.008 | 16.2 | 0.008 | 0.020 | - | - | 0.11 | 0.16 | - | - | 0.01 | 0.10 | - | 0.050 | 0.010 | The inventive example | |
| 35 | 0.005 | 0.06 | 0.18 | 0.02 | 0.004 | 17.8 | 0.008 | 0.030 | 1.45 | - | 0.12 | 0.23 | - | - | - | - | - | 0.035 | 0.014 | The inventive example | |
| 36 | 0.004 | 0.07 | 0.19 | 0.03 | 0.005 | 18.1 | 0.009 | 0.020 | 1.38 | - | 0.12 | 0.19 | 0.01 | 0.0011 | 0.01 | 0.11 | - | 1.028 | 0.013 | The inventive example | |
| 37 | 0.011 | 0.31 | 0.47 | 0.03 | 0.009 | 17.7 | 0.015 | 0.002 | - | - | 0.13 | - | 0.44 | - | 0.01 | 0.10 | - | 0.046 | 0.010 | The inventive example | |
| 38 | 0.008 | 0.47 | 0.14 | 0.02 | 0.002 | 19.1 | 0.014 | 0.019 | - | 0.55 | 0.38 | - | - | - | - | - | - | 0.022 | 0.020 | The inventive example | |
| 39 | 0.011 | 0.49 | 0.51 | 0.03 | 0.004 | 11.4 | 0.008 | 0.033 | - | - | 0.11 | 0.16 | - | - | - | - | - | 0.030 | 0.011 | The inventive example | |
| 40 | 0.06 | 0.30 | 0.61 | 0.03 | 0.003 | 16.1 | 0.041 | 0.002 | - | - | 0.18 | - | - | - | - | - | - | - | - | Comparative example | |
| 41 | 0.05 | 0.33 | 0.60 | 0.02 | 0.002 | 16.3 | 0.028 | 0.001 | - | - | 0.21 | - | - | - | - | - | - | 1.12 | 0.011 | Comparative example | |
| 42 | 0.0004 | 0.001 | 0.001 | 0.001 | 0.0003 | 16.2 | 0.0008 | 0.0005 | - | - | - | - | - | - | - | - | - | 0.021 | - | The inventive example | |
| 43 | 0.06 | 0.30 | 0.60 | 0.03 | 0.002 | 16.3 | 0.035 | 0.002 | - | - | 0.10 | - | - | - | - | - | - | 0.008 | 0.009 | The inventive example | |
| 44 | 0.06 | 0.30 | 0.59 | 0.03 | 0.003 | 16.2 | 0.044 | 0.002 | - | - | 0.31 | - | - | - | - | - | - | 0.260 | 0.37 | The inventive example | |
| 45 | 0 06 | 0.31 | 0.61 | 0.03 | 0.006 | 17.5 | 0.01 | 0.002 | - | - | 0.10 | - | - | - | - | - | - | 0.35 | 0.02 | Comparative example | |
Table 3
| Grade of steel No | Kind | Continuous speed m/min | The silver oxide amount | The surface smoothness state | Corrosion resistance | Anti-microbial property | Remarks | |||
| The area that gets rusty (%) | Before the corrosion resistance | After the corrosion resistance | ||||||||
| (wt％) | Aerobic plate count (cfu/ piece) | Bacteria reducing rate (%) | Aerobic plate count (cfu/ piece) | Bacteria reducing rate (%) | ||||||
| 11 | Austenite | 1.0 | 0.020 | 2B | 3 | ＜10 | ＞99.9 | 1.4×10 4 | 99.5 | The inventive example |
| 12 | 1.0 | 0.019 | BA | 0 | ＜10 | ＞99.9 | ＜10 | ＞99.9 | The inventive example | |
| 1.0 | 0.019 | 2B | 2 | ＜10 | ＞99.9 | ＜10 | ＞99.9 | The inventive example | ||
| 1.0 | 0.019 | #320 | 9 | ＜10 | ＞99.9 | ＜10 | ＞99.9 | The inventive example | ||
| 0.7 | 0.0004 | 2B | 17 | 6.7×10 4 | 97.4 | 9.2×10 4 | 96.7 | Comparative example | ||
| 1.8 | 0.0002 | 2B | 19 | 2.1×10 5 | 87.5 | 2.3×10 5 | 87.6 | Comparative example | ||
| 13 | 1.1 | - | 2B | 5 | 2.6×10 6 | 0 | 2.8×10 5 | 0 | Comparative example | |
| 14 | 1.2 | 0.007 | 2B | 2 | 1.1×10 3 | ＞99.9 | 1.3×10 3 | ＞99.9 | The inventive example | |
| 15 | 1.5 | 0.024 | 2B | 3 | ＜10 | ＞99.9 | ＜10 | ＞99.9 | The inventive example | |
| 16 | 1.2 | 0.040 | 2B | 25 | ＜10 | ＞99.9 | 3.0×10 5 | 89.3 | Comparative example | |
| 17 | 1.2 | 0.040 | 2B | 3 | ＜10 | ＞99.9 | 2.8×10 4 | 99.0 | The inventive example | |
| 18 | 1.2 | 0.040 | 2B | 18 | ＜10 | ＞99.9 | 3.0×10 6 | 89.3 | Comparative example | |
| 21 | Martensitic | 0.9 | 0.021 | #400 | 5 | ＜10 | ＞99.9 | 3.9×10 4 | 99.5 | The inventive example |
| 22 | 0.9 | 0.023 | #400 | 3 | ＜10 | ＞99.9 | 3.9×10 4 | 99.5 | The inventive example | |
| 1.7 | 0.0001 | #400 | 8 | 7.0×10 5 | 90.3 | 7.0×10 5 | 91.4 | Comparative example | ||
| 23 | 1.0 | - | #400 | 6 | 7.2×10 5 | 0 | 8.1×10 6 | 0 | Comparative example | |
| 24 | 1.0 | 0.008 | #400 | 4 | 2.3×10 3 | ＞99.9 | 1.3×10 3 | ＞99.9 | The inventive example | |
| 25 | 1.0 | 0.039 | #400 | 5 | ＜10 | ＞99.9 | ＜10 | ＞99.9 | The inventive example | |
| 26 | 1.0 | 0.041 | #400 | 89 | ＜10 | ＞99.9 | 8.3×10 5 | 89.8 | Comparative example | |
| 27 | 1.1 | 0.025 | #400 | 17 | ＜10 | ＞99.9 | ＜10 | ＞99.9 | The inventive example | |
| 28 | 1.0 | 0 019 | #400 | 18 | ＜10 | ＞99.9 | ＜10 | ＞99.9 | The inventive example | |
| 29 | 1.2 | 0.010 | #400 | 17 | 2.5×10 4 | 99.7 | 3.9×10 4 | 99.5 | The inventive example | |
Table 4
| Grade of steel No | Kind | Continuous speed m/min | The silver oxide amount | The surface smoothness state | Corrosion resistance | Anti-microbial property | Remarks | |||
| The area that gets rusty (%) | Before the corrosion resistance | After the corrosion resistance | ||||||||
| (wt％) | Aerobic plate count (cfu/ piece) | Bacteria reducing rate (%) | Aerobic plate count (cfu/ piece) | Bacteria reducing rate (%) | ||||||
| 31 | Ferrite | 1.2 | 0.028 | 2B | 7 | ＜10 | ＞99.9 | 1.5×10 4 | 99.5 | The inventive example |
| 32 | 1.1 | 0.031 | BA | 2 | ＜10 | ＞99.9 | ＜10 | ＞99.9 | The inventive example | |
| 1.1 | 0.031 | 2B | 6 | ＜10 | ＞99.9 | ＜10 | ＞99.9 | The inventive example | ||
| 1.1 | 0.031 | #320 | 9 | ＜10 | ＞99.9 | ＜10 | ＞99.9 | The inventive example | ||
| 0.7 | 0.11 | 2B | 27 | 3.2×10 4 | 98.9 | 3.9×10 5 | 87.0 | Comparative example | ||
| 1.8 | 0.0002 | 2B | 21 | 3.5×10 5 | 87.5 | 3.7×10 5 | 87.6 | Comparative example | ||
| 33 | 0.9 | 0.012 | 2B | 5 | 2.1×10 2 | ＞99.9 | 2.5×10 2 | ＞99.9 | The inventive example | |
| 34 | 1.3 | 0.038 | 2B | 4 | ＜10 | ＞99.9 | ＜10 | ＞99.9 | The inventive example | |
| 35 | 1.5 | 0.024 | 2B | 3 | ＜10 | ＞99.9 | ＜10 | ＞99.9 | The inventive example | |
| 36 | 1.5 | 0.018 | 2B | 3 | 5.2×10 1 | ＞99.9 | 8.3×10 1 | ＞99.9 | The inventive example | |
| 37 | 1.2 | 0.033 | BA | 0 | ＜10 | ＞99.9 | ＜10 | ＞99.9 | The inventive example | |
| 38 | 1.0 | 0.013 | 2B | 0 | 2.2×10 2 | ＞99.9 | 2.9×10 2 | ＞99.9 | The inventive example | |
| 39 | 1.2 | 0.015 | 2B | 15 | ＜10 | ＞99.9 | ＜10 | ＞99.9 | The inventive example | |
| 40 | 1.1 | - | 2B | 8 | 2.8×10 6 | 0 | 3.0×10 6 | 0 | Comparative example | |
| 41 | 0.9 | 0.040 | 2B | 73 | ＜10 | ＞99.9 | 4.5×10 5 | 85.0 | Comparative example | |
| 42 | 1.0 | 0.022 | BA | 0 | ＜10 | ＞99.9 | 2.7×10 2 | ＞99.9 | The inventive example | |
| 43 | 1.1 | 0.006 | BA | 3 | 1.2×10 3 | ＞99.9 | 1.3×10 3 | ＞99.9 | The inventive example | |
| 44 | 1.3 | 0.031 | BA | 4 | 1.8×10 2 | ＞99.9 | 1.5×10 4 | 99.5 | The inventive example | |
| 45 | 1.5 | 0.034 | 2B | 56 | 1.4×10 2 | ＞99.9 | 2.0×10 2 | ＞99.9 | Comparative example | |
Claims (9)
1. the stainless steel with anti-microbial property contains
The chromium that 10% (weight) is above,
The silver of 0.001-0.30% (weight) and
The silver suboxide that 0.0005% (weight) is above, the content of this silver suboxide is below 1.1 times of silver content.
2. the stainless steel with anti-microbial property of claim 1 also contains the vanadium of 0.001-1.0% (weight).
3. claim 1 and one of 2 the stainless steel with anti-microbial property also contain the following sulphur of 0.015% (weight).
4. each the stainless steel with anti-microbial property of claim 1-3, wherein silver content is 0.001% (weight) to less than 0.05% (weight).
5. the stainless steel with anti-microbial property of claim 2, wherein content of vanadium is 0.001-0.30% (weight).
6. the stainless steel with anti-microbial property of each of claim 1-5, wherein this stainless form is any in sheet material, band, tubing and the wire rod.
7. a manufacturing has the method for the stainless steel raw material of anti-microbial property, comprises the following steps:
In the fusion stainless steel, control chromium content, 0.001-0.30% (weight) silver content and the sulphur content below 0.015% (weight) more than 10% (weight);
And with 0.8-1.6 rice/minute casting speed continuous casting fused stainless steel.
8. the manufacturing of claim 7 has the stainless method of anti-microbial property, and wherein the fused stainless steel also contains the vanadium of 0.001-1.0% (weight).
9. claim 7 and one of 8 manufacturing have the stainless method of anti-microbial property, also comprise hot rolling and cold rolling step.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15809198 | 1998-06-05 | ||
| JP158091/1998 | 1998-06-05 | ||
| JP158091/98 | 1998-06-05 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1272889A true CN1272889A (en) | 2000-11-08 |
| CN1097098C CN1097098C (en) | 2002-12-25 |
Family
ID=15664110
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99800934A Expired - Fee Related CN1097098C (en) | 1998-06-05 | 1999-06-03 | Stainless steel product having excellent antimicrobial activity and method for production thereof |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US6306341B1 (en) |
| EP (1) | EP1018564B1 (en) |
| KR (1) | KR100404675B1 (en) |
| CN (1) | CN1097098C (en) |
| CA (1) | CA2297091A1 (en) |
| DE (1) | DE69940148D1 (en) |
| TW (1) | TW444060B (en) |
| WO (1) | WO1999064640A1 (en) |
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| CN1304627C (en) * | 2004-04-30 | 2007-03-14 | 麦桥 | Surface antibiotic, wearable stainless steel products and its production method |
| CN102327080A (en) * | 2011-07-28 | 2012-01-25 | 广东联塑科技实业有限公司 | Stainless steel sink |
| CN102534410A (en) * | 2012-02-24 | 2012-07-04 | 宝山钢铁股份有限公司 | Silver-containing austenitic antimicrobial stainless steel and manufacturing method thereof |
| CN106756600A (en) * | 2016-12-19 | 2017-05-31 | 浙江安胜科技股份有限公司 | A kind of stainless steel antibacterial cool-bag |
| CN112322986A (en) * | 2020-11-20 | 2021-02-05 | 宝钢德盛不锈钢有限公司 | Antibacterial austenitic stainless steel |
| TWI721924B (en) * | 2019-07-31 | 2021-03-11 | 日商杰富意鋼鐵股份有限公司 | Austenitic Iron-Fertilizer Iron Series Two-phase Stainless Steel Plate |
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| US6929705B2 (en) | 2001-04-30 | 2005-08-16 | Ak Steel Corporation | Antimicrobial coated metal sheet |
| JP2003021012A (en) * | 2001-07-10 | 2003-01-24 | Futaba Industrial Co Ltd | Fuel tank and producing method thereof |
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| US11761068B2 (en) | 2019-11-22 | 2023-09-19 | Blue Point Materials Research LLC | 3D printable stainless steel alloy with antibacterial properties for orthopedic implants |
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Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1083842B (en) * | 1954-07-28 | 1960-06-23 | Mannesmann Ag | Process for treating high-alloy steel powder, in particular chrome or chrome-nickel steel powder |
| BE712157A (en) * | 1967-03-15 | 1968-07-15 | ||
| DE69410555T2 (en) * | 1993-09-03 | 1999-01-28 | Sumitomo Metal Ind | Non-magnetic iron alloy with excellent corrosion resistance and machinability |
| JPH09249948A (en) * | 1996-03-13 | 1997-09-22 | Nisshin Steel Co Ltd | Stainless steel excellent in antibacterial property and designing property |
| JP3710589B2 (en) * | 1997-03-19 | 2005-10-26 | 日新製鋼株式会社 | Ag-containing antibacterial stainless steel sheet and manufacturing method |
| JP3706219B2 (en) * | 1997-03-19 | 2005-10-12 | 日新製鋼株式会社 | Austenitic antibacterial stainless steel containing Ag and Cu |
| JPH1129879A (en) * | 1997-05-12 | 1999-02-02 | Mitsubishi Materials Corp | Antibacterial treated metallic material and the antibacterial treatment |
| JP3227405B2 (en) * | 1997-06-25 | 2001-11-12 | 川崎製鉄株式会社 | Ferritic stainless steel with excellent antibacterial properties |
-
1999
- 1999-06-02 TW TW088109158A patent/TW444060B/en active
- 1999-06-03 KR KR10-2000-7000831A patent/KR100404675B1/en not_active IP Right Cessation
- 1999-06-03 DE DE69940148T patent/DE69940148D1/en not_active Expired - Lifetime
- 1999-06-03 CA CA002297091A patent/CA2297091A1/en not_active Abandoned
- 1999-06-03 WO PCT/JP1999/002972 patent/WO1999064640A1/en active IP Right Grant
- 1999-06-03 CN CN99800934A patent/CN1097098C/en not_active Expired - Fee Related
- 1999-06-03 EP EP99923888A patent/EP1018564B1/en not_active Expired - Lifetime
- 1999-06-03 US US09/463,830 patent/US6306341B1/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304627C (en) * | 2004-04-30 | 2007-03-14 | 麦桥 | Surface antibiotic, wearable stainless steel products and its production method |
| CN102327080A (en) * | 2011-07-28 | 2012-01-25 | 广东联塑科技实业有限公司 | Stainless steel sink |
| CN102534410A (en) * | 2012-02-24 | 2012-07-04 | 宝山钢铁股份有限公司 | Silver-containing austenitic antimicrobial stainless steel and manufacturing method thereof |
| CN106756600A (en) * | 2016-12-19 | 2017-05-31 | 浙江安胜科技股份有限公司 | A kind of stainless steel antibacterial cool-bag |
| TWI721924B (en) * | 2019-07-31 | 2021-03-11 | 日商杰富意鋼鐵股份有限公司 | Austenitic Iron-Fertilizer Iron Series Two-phase Stainless Steel Plate |
| CN112322986A (en) * | 2020-11-20 | 2021-02-05 | 宝钢德盛不锈钢有限公司 | Antibacterial austenitic stainless steel |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2297091A1 (en) | 1999-12-16 |
| US6306341B1 (en) | 2001-10-23 |
| EP1018564B1 (en) | 2008-12-24 |
| WO1999064640A1 (en) | 1999-12-16 |
| KR100404675B1 (en) | 2003-11-07 |
| DE69940148D1 (en) | 2009-02-05 |
| CN1097098C (en) | 2002-12-25 |
| EP1018564A1 (en) | 2000-07-12 |
| KR20010022258A (en) | 2001-03-15 |
| EP1018564A4 (en) | 2002-03-20 |
| TW444060B (en) | 2001-07-01 |
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